Azo dyestuffs insoluble in water and fiber dyed therewith



Patented Aug. 16, 1938 UNITED STATES PATENT OFFICE AZO DYESTUFFS IN SOLUBLE IN WATER AND FIBER DYED THEREWI TH Fritz Miiller, Willy Schumachenand Otto Scherer,

Frankfort-on-the-Main,

Germany, assignors to General Aniline Works, Inc.,New York, N. Y., a corporation of Delaware No Drawing. Application October 28, 1937. Se-

rial No. 171,476. In Germany. October 30,

12 Claims. 01. aco-203')" The present invention relates to aZo-dyestuffs insoluble in waterand to fiber dyed therewith; more particularly, it'relates' to dyestuifs of the following general formula? sbzom wherein the nucleus R may contain further substituents.

We have found thatdyestuifs of technically valuable tints and good properties of fastness are obtainable by coupling a diazonium compound from an amino-substitution product of trifiuoromethylphenylsulphone corresponding with the following formula:

Q-Somm or from a substitution product thereof which does not contain any group lending solubility, with a 2,3-hydroxynaphthoic acid arylide.

The dyestuffs may be produced in substance, on the fiber or on a substratum adapted for the production of lakes. v

When produced on the fiber, the dyestuffs are subject to the known high demands in respect of resistance to alkaline agents and it is surprising that the trifluoromethylsulphone group present in the dyestuif molecule and consisting of two strongly negative radicals is not only stable to the alkaline treatment but also improves the properties of the dyeings.

The new dyestuffs are particularly distinguished by their very good fastness to light. In this respect they surpass the known water-insoluble azodyestuffs obtainable by coupling diazotized aminobenzenealkylsulphones or diazotized aminotrifluoromethylbenzenes with 2.3-hydrox ynaphthoic acid arylides.

The aminophenyltrifluoromethylsulphones used in this process as diazo-components may be prepared by reductionofthe trifiuoromethylphenylsulphones substituted by a nitro-group and ob tainable as described in U. S. Patent No. 2,108,-

606; issued February 15, 1938, or by reduction of the nitro-compounds made by nitration of trifiuoromethylphenylsulphones. The orthoand para-amino derivatives are suitably prepared by causing nitric acid to act in the presence of sul phuric acid ontrifluorornethylphenylsulphides obtainable as described in U. S. Patent No. 2,108,606, oxidizing the nitrophenyltrifluoromethylsulphoxides formed and reducing the nitrated sulphone's thus obtained.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto:

- (l)- Grounding liquor 4 grams of 1-(2.3-hydroxynaphthoylamino)- 2.4-dimethoxy-5-chlorobenzene are dissolved in a mixture of 6 cc. of alcohol, 2 cc. of pyridine, 2 cc.of caustic soda solution of 34 B. and 6 cc. of water with addition of 2 cc. of a formaldehyde solution of 30 per cent. strength. This solution is introduced into a bath containing 10 cc. of Turkey red oil of 50 per cent. strength and 10 cc. of causticsoda solution of 34 Be. in 1000 cc. of water at 30 C.

Developing solution the grams ofsodium chloride the whole is made up} to cc. by means of water.

Dyeing process 50 grams of cotton are treatedfor half an hour at C. in the grounding liquor. The whole is then well centrifuged and dyed for half an hour in the developing solution; the material is subsequently rinsed, soaped at boiling temperature, rinsed again and dried. A yellowish red dyeing of very good fastness to light is obtained. The

OCHa

CONHOOOHa (2) While well stirring, a solution of 29.5 parts by weight of 1-(2.3'-hydroxynaphthoylamino)- 2-methoxybenzene rendered alkaline by means of caustic soda and to which there has been added the amount of sodium acetate solution necessary for binding the excess of mineral acid, is caused to run slowly into a diazo-solution prepared in the usual manner from 22.5 parts by weight of B-aminophenyl-l-trifluoromethylsulphone. After formation of the dyestuff is finished, the whole is filtered with suction and washed well. The dyestuff is advantageously worked up into the form of a paste. When mixed with one of the usual substrata, it yields an orange-red lake having very good properties of fastness. The dyestuff may also be prepared by mixing the diazo solution with a substratum, for instance, barytes, zinc White or the like, and running in the arylide solution.

(3) A cotton fabric is padded with a solution containing 13.2 grams of 1-(2,3-hydroxynaphthoylamino) -benzene 20 grams of Turkey red oil, and

20 cc. of caustic soda solution of 32.5 per cent. strength and made up to 1 litre and is then dried. Thereupon, the fabric is printed with a printing paste prepared as follows: The solid diazonium compound from 12.7 grams of 4-methoxy- 3 -aminophenyl-1- trifluoromethylsulphone is dissolved in 10 cc. of acetic acid of per cent.

strength and 400 cc. of water; the Whole is thickened by means of 400 grams of starch tragacanth thickening and made up to 1 litre.

After printing, the fabric is dried, then treated with a hot sodium carbonate solution (10 grams per litre) rinsed while cold, soaped at boiling temperature, rinsed again, dried and Worked up. A print having a vivid red tint is obtained.

The following table includes a number of other azo-dyestuffs obtainable according to the present invention:

Diazo-compound irom Coupled with Tint 1-(2,3-hydroxynaphthoylamina)- (l) 4-methoxy-3-aminophenyl-l-trifluoromethylsulphone 2-methyl-i-methoxybenezene. Yellowish red. (2) 4-Inethoxy3-aminophenyl-l-trifluoromethy1sl1lph0ne 3methyl-truethoxybenzene. Do. (3) 4-n1ethoxy-3-aminophenyl-l-trifluoromethylsulphone 2-i'nethoxybenzene Scarlet. (4) 4-methoxy-3-aniinophenyl-l-trifiuoromethylsulphone 4-methoxybenzene Yellowish red. (5) 4 methoxy 3 aminophenyl Benzene Vivid middle-red.

2-methyl D0. (7) 4-methoxy-3-armnophenyl-1-tr1fluoromethylsulphone 2-methoxy-S-chlorobenzene Scarlet. (8) 4-methoxy-3-arninophenyl-l-trifluoromethylsulphone 2, 5-d1methoxy-i-chlorobenzene.. Yellowzsh red. (9) 4-inethoxy-3-aminophenyl-l-trifluoromethylsulphone 2-ethoxybenzene carlet.

0) 4-methoxy-3aminophenyl-l-trifluoromethylsulphone. Naphthalene V1vid bluish red. (11) 4-meth0xy-3-aminophenyl-1-trifluoromethylsulphone 4-chl0robenzen Do. (12) 4-ethoxy-3-aminophenyl-l-trifluoromethylsulphone Benzene Middle-red. (13) 3-aminophenyl-l-trifluoromethylsulphone 2, 4-dimethoxy lorobenzene," Brown-red. (l4) 3-aminophenyl-l-trifiuoromethylsulphone Z-methoxybenzene Red-orange. (l5) -methyl-B-aminophenyl-l-triliuoromethylsulphone 2-rnethoxybenzene. Vivid red-orange. (l6) 4-methyl-3-aminophenyl-l-trifluoromethylsulphone 3-rnethyl-4-methoxybenzen Brick-red. (l7) 4-ch1oro-3-aminophenyl-l-trifluorornethylsulphone..r 2-methoxybenzene Orange. (18) 4 chlor0-3-aminopheny1-l-trifiuoromethylsulphone Z-methylbenzene Red-orange. (l9) 4-chloro-3-aminophenyl-l-triflnoromethylsulplione 4-cl1lor0benzene- D0. (20) 4-bromo-3-aininophenyl-l-trifiuoromethylsulphone 2-methoxybenzene Orange. (21) 5-chl0ro-2-aminopheny1-l-triiiuoromethylsulphone 3-methyl-4-methoxybenzene Yellow-red. (22) 5-chlor0-2-aminophenyl-l-trifiuoromethylsulphone 4-chlor0benzene..- Yellowish scarlet. (23) 4-aminophenyl-l-triiluoroniethylsulphone Z-methoxybenzene Scarlet. (24) 4-aminophenyl-1-trifluoromethylsulphone 4-methoxybenzene Brownish red. (25)h3-aminophenyl-4-methylsulphonel-trifluoromethylsul- Benzene. Golden-yellow.

1) one. (26) 3-arninophenyli ethylsulphone-1-trifluoromethy1su lphone. Benzene n Do.

(27) 4-methoxy-3-aminophonyl-l-tritluoromethylsulphone (28) 4-methyl-2-aminophenyl-l-triflnoromethy nl me Nnnhihalene Naphthalene Yellowish scarlet.

Vivid scarlet.

1-(2, 3-hydrozynaphthoylamino)- (29) imethyl-2-aminophenyl-1-trifluoromethylsulphone. (30) 2-chloro-5-arninophenyl-l-trifluoromethylsul ne 4-dich1oro-G-aminophenyl-1-triflu0romethylsulphon i-chlorobenzene 2-rnethyl-4 ch1orobenzene Yellowish scarlet.

Berwone Scarlet. z-methoxybenzene Covered red. 2-methyl-4-chlorobcnzene. Bluish red.

Vivid red-orange.

2-2, 3'-hydrozy'naphthoylamino)- (34) 3, 4-dichloro-G-aminophenyl-l-trifluoromethylsulphone Naphthalene Scarlet.

1-(2, 3-hydrozymphthoylamino)- (35) 2,4-dibromo-6-aminophenyl-l-trlfluoromethylsulphone- Z-methoxybenzene Red.

(36) 2,4-dimethoxy-5-aminophenyl-l-trifluoromethylsulphone 2'methyl-4-chlorobenzene Ruby-red.

(37) 2, 4-dimethoxy-5-aminophenyl-l-tnfluoromethylsulphone 2, 4-dimethoxy-5-chlorobenzene. Do.

(38) 2, 4-diethoxy-5-aminophenyl-l-trifluoromethylsulphone 2-4-dimethoxy-5-chlorobenzene Do.

(39) 2, 5-d1ohloro4-aminophenyl-l-tritluoromethylsulphone 3-nitrobenzene Brick-red.

Since an object of the present invention is to provide dyestufis of good fastness properties which dyestuffs are insoluble in water and a1- kalies, it is to be understod that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies andto tend to depreciate the fastness of the dyestuifs to alkalies. Substituents of this kind are, for instance, the sulphonic and the carboxylic acid group.

We claim:

1. The water-insoluble azo-dyestuffs of the following general formula:

X2 X1 I l N=N- \m l SOzCFa QONELR wherein X1 stands .for a member of the group consisting of hydrogen, halogen and alkoxy, X2 for a member of the group consisting of hydrogen, halogen, methyl, alkoxy and alkylsulphonyl, and R means a member of the group consisting of radicals of the benzene and naphthalene series, yielding, when produced on the fiber, goldenyellow to ruby-red shades of good fastness properties, particularly of very good fastness to light.

2. The water insoluble azo-dyestuifs of the following general formula:

OH scion \OONELR wherein X stands for a member of the group consisting of hydrogen, halogen, methyl, alkoxy and alkylsulphonyl, and R means a member of the group consisting of radicals of the benzene and. naphthalene series, yielding, when produced on the fiber, golden-yellow to red shades of good fastness properties, particularly of very good fastness to light.

3. The water-insoluble lowing general formula:

0 .alkyl OH OzCFs \OONH.R wherein R. means a radical of the benzene seazo-dyestufis of the folries, yielding, when produced on the fiber, scarlet to red shades of good fastness properties, particularly of very good fastness to light.

4. The water-insoluble azo-dyestuff of the following formula:

OCHs yielding, when produced on the fiber, yellowishred shades of good fastness properties, particularly of very good fastness to light.

5. The water-insoluble azo-dyestufi" of the following formula:

OCH3

SOzOFa c ONE-O yielding, when produced on the fiber, vivid middle-red shades of good fastness properties, particularly of very good fastness to light.

6. The water-insoluble azo-dyestuff of the following formula:

OCH:

o ONE-Q01 SOzOFa dyestuffs as claimed in dyestufi as claimed in dyestuff as claimed FRITZ WILLY SCHUMACHER. OTTO SCHERER. 

